Morphological Study before and after Thermal Treatment of Polymer-Polymer Mixed-Matrix Membranes for Gas Separations.

A good integration of the polymer materials that form a mixed-matrix membrane (MMM) for gas separation is essential to reaching interesting permselective properties. In this work, a porous polymer network (PPN), obtained by combining triptycene and trifluoroacetophenone, has been used as a filler, which was blended with two o-hydroxypolyamides (HPAs) that act as polymer matrices. These polymer matrices have been thermally treated to induce a thermal rearrangement (TR) of the HPAs to polybenzoxazoles (ß-TR-PBOs) through a solid-state reaction. For its structural study, various techniques have been proposed that allow us to undertake a morphological investigation into the integration of these materials. To access the internal structure of the MMMs, three different methods were used: a polishing process for the material surface, the partial dissolution of the polymer matrix, or argon plasma etching. The argon plasma technique has not only revealed its potential to visualize the internal structure of these materials; it has also been proven to allow for the transformation of their permselective properties. Force modulation and phase contrast in lift-mode techniques, along with the topographic images obtained via the tapping mode using a scanning probe microscope (SPM), have allowed us to study the distribution of the filler particles and the interaction of the polymer and the filler. The morphological information obtained via SPM, along with that of other more commonly used techniques (SEM, TGA, DSC, FTIR, WASX, gas adsorption, and permeability measurements), has allowed us to postulate the most probable structural configuration in this type of system.

Mixed Matrix Membranes Using Porous Organic Polymers (POPs)-Influence of Textural Properties on CO2/CH4 Separation.

Mixed matrix membranes (MMMs) provide the opportunity to test new porous materials in challenging applications. A series of low-cost porous organic polymer (POPs) networks, possessing tunable porosity and high CO2 uptake, has been obtained by aromatic electrophilic substitution reactions of biphenyl, 9,10-dihydro-9,10-dimethyl-9,10-ethanoanthracene (DMDHA), triptycene and 1,3,5-triphenylbenzene (135TPB) with dimethoxymethane (DMM). These materials have been characterized by FTIR, 13C NMR, WAXD, TGA, SEM, and CO2 uptake. Finally, different loadings of these POPs have been introduced into Matrimid, Pebax, and chitosan:polyvinyl alcohol blends as polymeric matrices to prepare MMMs. The CO2/CH4 separation performance of these MMMs has been evaluated by single and mixed gas permeation experiments at 4 bar and room temperature. The effect of the porosity of the porous fillers on the membrane separation behavior and the compatibility between them and the different polymer matrices on membrane design and fabrication has been studied by Maxwell model equations as a function of the gas permeability of the pure polymers, porosity, and loading of the fillers in the MMMs. Although the gas transport properties showed an increasing deviation from ideal Maxwell equation prediction with increasing porosity of the POP fillers and increasing hydrophilicity of the polymer matrices, the behavior of biopolymer-based CS:PVA MMMs approached that of Pebax-based MMMs, giving scope to not only new filler materials but also sustainable polymer choices to find a place in membrane technology.

Palladium Catalysts Supported in Microporous Phosphine Polymer Networks.

A new set of microporous organic polymers (POPs) containing diphosphine derivatives synthesized by knitting via Friedel-Crafts has been attained. These amorphous three-dimensional materials have been prepared by utilizing diphosphines, 1,3,5-triphenylbenzene, and biphenyl as nucleophile aromatic groups, dimethoxymethane as the electrophilic linker, and FeCl3 as a promoting catalyst. These polymer networks display moderate thermal stability and high microporosity, boasting BET surface areas above 760 m2/g. They are capable of coordinating with palladium acetate, using the phosphine derivative as an anchoring center, and have proven to be highly efficient catalysts in Suzuki-Miyaura coupling reactions involving bromo- and chloroarenes under environmentally friendly (using water and ethanol as solvents) and aerobic conditions. These supported catalysts have achieved excellent turnover numbers (TON) and turnover frequencies (TOF), while maintaining good recyclability without significant loss of activity or Pd leaching after five consecutive reaction cycles.

Isomeric Aromatic Polyimides Containing Biphenyl Moieties for Gas Separation Applications.

An optimized synthesis of the monomer 2,2'3,3'-biphenyltetracarboxylic dianhydride, iBPDA, was performed to obtain high molecular weight polymers. This monomer has a contorted structure that produces a non-linear shape, hindering the packing of the polymer chain. Aromatic polyimides of high molecular weight were obtained by reaction with the commercial diamine 2,2-bis(4-aminophenyl) hexafluoropropane, 6FpDA, which is a very common monomer in gas separation applications. This diamine has hexafluoroisopropylidine groups which introduce rigidity in the chains, hindering efficient packing. The thermal treatment of the polymers processed as dense membranes had two targets: on the one hand, to achieve the complete elimination of the solvent used, which could remain occluded in the polymeric matrix, and on the other hand to ensure the complete cycloimidization of the polymer. A thermal treatment exceeding the glass transition temperature was performed to ensure the maximum degree of imidization at 350 °C. The good mechanical properties of these materials allow for their use in high-pressure gas purification applications. Moreover, models of the polymers exhibited an Arrhenius-like behavior characteristic of secondary relaxations, normally associated with local motions of the molecular chain. The gas productivity of these membranes was high.

New Insights in the Synthesis of High-Molecular-Weight Aromatic Polyamides-Improved Synthesis of Rod-like PPTA.

By employing a variation of the polyamidation method using in situ silylated diamines and acid chlorides, it was possible to obtain a rod-type polyamide: poly(p-phenylene terephthalamide) (PPTA, a polymer used in the high-value-added material Kevlar), with a molecular weight much higher than that obtained with the classical and industrial polyamidation method. The optimization of the method has consisted of using, together with the silylating agent, a mixture of pyridine and a high-pKa tertiary amine. The research was complemented by a combination of nuclear magnetic resonance and molecular simulation studies, which determined that the improvements in molecular weight derive mainly from the formation of silylamide groups in the growing polymer.

Aromatic Polyimide Membranes with tert-Butyl and Carboxylic Side Groups for Gas Separation Applications-Covalent Crosslinking Study.

A set of aromatic copolyimides was obtained by reaction of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), and mixtures of the diamines 1,4-bis(4-amino-2-trifluoromethylphenoxy)-2,5-di-tert-butylbenzene (CF3TBAPB) and 3,5-diamino benzoic acid (DABA). These polymers were characterized and compared with the homopolymer derived from 6FDA and CF3TBAPB. All copolyimides showed high molecular weight values and good mechanical properties. The presence of carboxylic groups in these copolymers allowed their chemical crosslinking by reaction with 1,4-butanediol. Glass transition temperatures (Tg) were higher than 260 °C, showing the non-crosslinked copolyimides had the highest Tg values. Degradation temperature of crosslinked copolyimides was lower than their corresponding non-crosslinked ones. Mechanical properties of all polymers were good, and thus, copolyimide (precursor, and crosslinked ones) films could be tested as gas separation membranes. It was observed that CO2 permeability values were around 100 barrer. Finally, the plasticization resistance of the crosslinked material having a large number of carboxylic groups was excellent.

Thermally Rearranged Mixed Matrix Membranes from Copoly(o-hydroxyamide)s and Copoly(o-hydroxyamide-amide)s with a Porous Polymer Network as a Filler-A Comparison of Their Gas Separation Performances.

Copoly(o-hydroxyamide)s (HPA) and copoly(o-hydroxyamide-amide)s (PAA) have been synthesized to be used as continuous phases in mixed matrix membranes (MMMs). These polymeric matrices were blended with different loads (15 and 30 wt.%) of a relatively highly microporous porous polymer network (PPN). SEM images of the manufactured MMMs exhibited good compatibility between the two phases for all the membranes studied, and their mechanical properties have been shown to be good enough even after thermal treatment. The WAX results show that the addition of PPN as a filler up to 30% does not substantially change the intersegmental distance and the polymer packing. It seems that, for all the membranes studied, the free volume that determines gas transport is in the high end of the possible range. This means that gas flow occurs mainly between the microvoids in the polymer matrix around the filler. In general, both HPA- and PAA-based MMMs exhibited a notable improvement in gas permeability, due to the presence of PPN, for all gases tested, with an almost constant selectivity. In summary, although the thermal stability of the PAA is limited by the thermal stability of the polyamide side chain, their mechanical properties were better. The permeability was higher for the PAA membranes before their thermal rearrangement, and these values increased after the addition of moderate amounts of PPN.

Free Volume and Permeability of Mixed Matrix Membranes Made from a Terbutil-M-terphenyl Polyamide and a Porous Polymer Network.

A set of thermally rearranged mixed matrix membranes (TR-MMMs) was manufactured and tested for gas separation. These membranes were obtained through the thermal treatment of a precursor MMM with a microporous polymer network and an o-hydroxypolyamide,(HPA) created through a reaction of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (APAF) and 5'-terbutil-m-terfenilo-3,3″-dicarboxylic acid dichloride (tBTmCl). This HPA was blended with different percentages of a porous polymer network (PPN) filler, which produced gas separation MMMs with enhanced gas permeability but with decreased selectivity. The thermal treatment of these MMMs gave membranes with excellent gas separation properties that did not show the selectivity decreasing trend. It was observed that the use of the PPN load brought about a small decrease in the initial mass losses, which were lower for increasing PPN loads. Regarding the glass transition temperature, it was observed that the use of the filler translated to a slightly lower Tg value. When these MMMs and TR-MMMs were compared with the analogous materials created from the isomeric 5'-terbutil-m-terfenilo-4,4″-dicarboxylic acid dichloride (tBTpCl), the permeability was lower for that of tBTmCl, compared with the one from tBTpCl, although selectivity was quite similar. This fact could be attributed to a lower rigidity as roughly confirmed by the segmental length of the polymer chain as studied by WAXS. A model for FFV calculation was proposed and its predictions compared with those evaluated from density measurements assuming a matrix-filler interaction or ideal independence. It turns out that permeability as a function of FFV for TR-MMMs follows an interaction trend, while those not thermally treated follow the non-interaction trend until relatively high PPN loads were reached.

Mixed Matrix Membranes Loaded with a Porous Organic Polymer Having Bipyridine Moieties.

Mixed matrix membranes (MMMs), derived from three aromatic polyimides (PIs), and an affordable porous organic polymer (POP) having basic bipyridine moieties were prepared. Matrimid and two fluorinated polyimides, which were derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and 2,2'-bis(4-aminophenyl)hexafluoropropane (6F6F) or 2,4,6-trimethyl-m-phenylenediamine (6FTMPD), were employed as polymer matrixes. The used POP was a highly microporous material (surface area of 805 m2 g-1) with excellent thermal and chemical stability. The MMMs showed good compatibility between the PIs and POP, high thermal stabilities and glass transition temperatures superior to those of the neat PI membranes, and good mechanical properties. The addition of POP to the matrix led to an increase in the gas diffusivity and, thus, in permeability, which was associated with an increase in the fractional free volume of MMMs. The increase in permeability was higher for the less permeable matrix. For example, at 30 wt.% of POP, the permeability to CO2 and CH4 of the MMMs increased by 4- and 7-fold for Matrimid and 3- and 4-fold for 6FTMPD. The highest CH4 permeability led to a decrease in CO2/CH4 selectivity. The CO2/N2 separation performance was interesting, as the selectivity remained practically constant. Finally, the POP showed no molecular sieving effect towards the C2H4/C2H6 and C3H6/C3H8 gas pairs, but the permeability increased by about 4-fold and the selectivity was close to that of the matrix. In addition, because the POP can form metal ion bipyridine complexes, modified POP-based MMMs could be employed for olefin/paraffin separations.

Gas Permeability, Fractional Free Volume and Molecular Kinetic Diameters: The Effect of Thermal Rearrangement on ortho-hydroxy Polyamide Membranes Loaded with a Porous Polymer Network.

Mixed-matrix membranes (MMMs) consisting of an ortho-hydroxy polyamide (HPA) matrix, and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (ß-TR-PBO). Two different HPAs were synthesized to be used as a matrix, 6FCl-APAF and tBTpCl-APAF, while the PPN used as a filler was prepared by reacting triptycene and trifluoroacetophenone. The permeability of He, H2, N2, O2, CH4 and CO2 gases through these MMMs are analyzed as a function of the fraction of free volume (FFV) of the membrane and the kinetic diameter of the gas, allowing for the evaluation of the free volume. Thermal rearrangement entails an increase in the FFV. Both before and after thermal rearrangement, the free volume increases with the PPN content very similarly for both polymeric matrices. It is shown that there is a portion of free volume that is inaccessible to permeation (occluded volume), probably due to it being trapped within the filler. In fact, permeability and selectivity change below what could be expected according to densities, when the fraction of occluded volume increases. A higher filler load increases the percentage of inaccessible or trapped free volume, probably due to the increasing agglomeration of the filler. On the other hand, the phenomenon is slightly affected by thermal rearrangement. The fraction of trapped free volume seems to be lower for membranes in which the tBTpCl-APAF is used as a matrix than for those with a 6FCl-APAF matrix, possibly because tBTpCl-APAF could approach the PPN better. The application of an effective medium theory for permeability allowed us to extrapolate for a 100% filler, giving the same value for both thermally rearranged and non-rearranged MMMs. The pure filler could also be extrapolated by assuming the same tendency as in the Robeson's plots for MMMs with low filler content.

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement.

Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (ß-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropyilidene moieties, 6FCl-APAF, while the PPN was prepared by reacting triptycene (TRP) and trifluoroacetophenone (TFAP) in a superacid solution. The most probable size of the PPN particles was 75 nm with quite large distributions. The resulting membranes were analyzed by SEM and AFM. Up to 30% PPN loads, both SEM and AFM images confirmed quite planar surfaces, at low scale, with limited roughness. Membranes with high hydrogen permeability and good selectivity for the gas pairs H2/CH4 and H2/N2 were obtained. For H2/CO2, selectivity almost vanished after thermal rearrangement. In all cases, their hydrogen permeability increased with increasing loads of PPN until around 30% PPN with ulterior fairly abrupt decreasing of permeability for all gases studied. Thermal rearrangement of the MMMs resulted in higher permeabilities but lower selectivities. For all the membranes and gas pairs studied, the balance of permeability vs. selectivity surpassed the 1991 Robeson's upper bound, and approached or even exceeded the 2008 line, for MMMs having 30% PPN loads. In all cases, the HPA-MMMs before thermal rearrangement provided good selectivity versus permeability compromise, similar to their thermally rearranged counterparts but in the zone of high selectivity. For H2/CH4, H2/N2, these nonthermally rearranged MMMs approach the 2008 Robeson's upper bound while H2/CO2 gives selective transport favoring H2 on the 1991 Robeson's bound. Thus, attending to the energy cost of thermal rearrangement, it could be avoided in some cases especially when high selectivity is the target rather than high permeability.

Gas Separation by Mixed Matrix Membranes with Porous Organic Polymer Inclusions within o-Hydroxypolyamides Containing m-Terphenyl Moieties.

A hydroxypolyamide (HPA) manufactured from 2,2-bis(3-amino-4-hydroxy phenyl)-hexafluoropropane (APAF) diamine and 5'-terbutyl-m-terphenyl-4,4''-dicarboxylic acid chloride (tBTpCl), and a copolyimide produced by stochiometric copolymerization of APAF and 4,4'-(hexafluoroisopropylidene) diamine (6FpDA), using the same diacid chloride, were obtained and used as polymeric matrixes in mixed matrix membranes (MMMs) loaded with 20% (w/w) of two porous polymer networks (triptycene-isatin, PPN-1, and triptycene-trifluoroacetophenone, PPN-2). These MMMs, and also the thermally rearranged membranes (TR-MMMs) that underwent a thermal treatment process to convert the o-hydroxypolyamide moieties to polybenzoxazole ones, were characterized, and their gas separation properties evaluated for H2, N2, O2, CH4, and CO2. Both TR process and the addition of PPN increased permeability with minor decreases in selectivity for all gases tested. Excellent results were obtained, in terms of the permeability versus selectivity compromise, for H2/CH4 and H2/N2 separations with membranes approaching the 2008 Robeson's trade-off line. The best gas separation properties were obtained when PPN-2 was used. Finally, gas permeation was characterized in terms of chain intersegmental distance and fraction of free volume of the membrane along with the kinetic diameters of the permeated gases. The intersegmental distance increased after TR and/or the addition of PPN-2. Permeability followed an exponential dependence with free volume and a quadratic function of the kinetic diameter of the gas.

Porous Organic Polymers Containing Active Metal Centers for Suzuki-Miyaura Heterocoupling Reactions.

A new generation of confined palladium(II) catalysts covalently attached inside of porous organic polymers (POPs) has been attained. The synthetic approach employed was straightforward, and there was no prerequisite for making any modification of the precursor polymer. First, POP-based catalytic supports were obtained by reacting one symmetric trifunctional aromatic monomer (1,3,5-triphenylbenzene) with two ketones having electron-withdrawing groups (4,5-diazafluoren-9-one, DAFO, and isatin) in superacidic media. The homopolymers and copolymers were made using stoichiometric ratios between the functional groups, and they were obtained with quantitative yields after the optimization of reaction conditions. Moreover, the number of chelating groups (bipyridine moieties) available to bind Pd(II) ions to the catalyst supports was modified using different DAFO/isatin ratios. The resulting amorphous polymers and copolymers showed high thermal stability, above 500 °C, and moderate-high specific surface areas (from 760 to 935 m2 g-1), with high microporosity contribution (from 64 to 77%). Next, POP-supported Pd(II) catalysts were obtained by simple immersion of the catalyst supports in a palladium(II) acetate solution, observing that the metal content was similar to that theoretically expected according to the amount of bipyridine groups present. The catalytic activity of these heterogeneous catalysts was explored for the synthesis of biphenyl and terphenyl compounds, via the Suzuki-Miyaura cross-coupling reaction using a green solvent (ethanol/water), low palladium loads, and aerobic conditions. The findings showed excellent catalytic activity with quantitative product yields. Additionally, the recyclability of the catalysts, by simply washing it with ethanol, was excellent, with a sp2-sp2 coupling yield higher than 95% after five cycles of use. Finally, the feasibility of these catalysts to be employed in tangible organic reactions was assessed. Thus, the synthesis of a bulky compound, 4,4'-dimethoxy-5'-tert-butyl-m-terphenylene, which is a precursor of a thermal rearrangement monomer, was scaled-up to 2 g, with high conversion and 96% yield of the pure product.

Microporous Polymer Networks for Carbon Capture Applications.

A new generation of porous polymer networks has been obtained in quantitative yield by reacting two rigid trifunctional aromatic monomers (1,3,5-triphenylbenzene and triptycene) with two ketones having electron-withdrawing groups (trifluoroacetophenone and isatin) in superacidic media. The resulting amorphous networks are microporous materials, with moderate Brunauer-Emmett-Teller surface areas (from 580 to 790 m2 g-1), and have high thermal stability. In particular, isatin yields networks with a very high narrow microporosity contribution, 82% for triptycene and 64% for 1,3,5-triphenylbenzene. The existence of favorable interactions between lactams and CO2 molecules has been stated. The materials show excellent CO2 uptakes (up to 207 mg g-1 at 0 °C/1 bar) and can be regenerated by vacuum, without heating. Under postcombustion conditions, their CO2/N2 selectivities are comparable to those of other organic porous networks. Because of the easily scalable synthetic method and their favorable characteristics, these materials are very promising as industrial adsorbents.

Soluble, microporous, Tröger's Base copolyimides with tunable membrane performance for gas separation.

A facile two-step synthesis beginning with commercial monomers to prepare copolyimides by Tröger's Base (TB) formation provides membranes for the first time with tunable gas transport relative to hydrogen separations, CO2 plasticization resistance, and good mechanical and thermal properties.

Reactivity of the 4-amino-5H-1,2-oxathiole-2,2-dioxide heterocyclic system: a combined experimental and theoretical study.

The reactivity of the 4-amino-5H-1,2-oxathiole-2,2-dioxide (or beta-amino-gamma-sultone) heterocyclic system has scarcely been studied. Here we describe the reactivity of this system towards electrophiles and amines on readily available model substrates differently substituted at the C-5 position. A variety of C-electrophiles, carbonyl electrophiles (such as acyl chlorides, isocyanates, or aldehydes) and halogen or nitrogen electrophiles have been explored. Both the C-3 and 4-amino positions of the beta-amino-gamma-sultone system are able to undergo electrophilic reactions, and the reaction products depend on the electrophile used and on the reaction conditions. On the other hand, nucleophilic attack of amines occurs at the C-4 position of the beta-amino-gamma-sultone system only in spiranic substrates bearing alicyclic substituents at the C-5 position. A comparative computational study between spiranic and non-spiranic substrates suggests that conformational changes, undergone on intermediate compounds, account for the observed reactivity differences. Moreover, these conformational changes seem to bring about an increase of electron density on the N-4 and C-3 atoms of the enaminic system, and a possible enhancement in the reactivity of spiranic substrates towards electrophiles in the presence of amines. Experimental data consistent with this predicted enhanced reactivity is also presented.